Triazine compounds and herbicides containing the same, and a process for the preparation thereof

ABSTRACT

wherein X represents chlorine or a methylthio group, R represents hydrogen or a C1 4 alkyl group, and R&#39;&#39; stands for a C1 4 alkyl or alkenyl group, of excellent herbicidal activities are prepared as follows: cyanurchloride is reacted with diacetonamine in a molar ratio of 1:1 in an aqueous or organic solvent medium in the presence of an acid binding agent, the thus-obtained 2,4-dichloro-6-( Alpha , Alpha -dimethyl- Beta -acetyl-ethylamino)-1,3,5-triazine is reacted with an amine of the general formula NHRR&#39;&#39; in the presence of an acid binding agent, and if a 2-methylthio compound is to be prepared, the thus-obtained 2-chloro-4-alkylamino-6-( Alpha , Alpha -dimethyl- Beta -acetyl-ethylamino)-1,3,5-triazine is reacted with thiourea and the obtained product is methylated, or the 2-chloro compound is reacted with methylthiol. 2-Substituted-4-alkylamino-6-( Alpha , Alpha -dimethyl- Beta acetyl-ethylamino-1,3,5-triazines of the general formula (I)

United States Patent 1 Matolcsy et a1.

145] July 1, 1975 TRIAZINE COMPOUNDS AND HERBICIDES CONTAINING THE SAME, AND A PROCESS FOR THE PREPARATION THEREOF [75] Inventors: Gyorgy Matolcsy; Barna Bordas;

Odon Szatala; Viktor Andriska, all of Budapest; Erzsebet Grega, nee Toth; Zoltan Pinter, both of Miskolc; Sandor Nagy, Putnok, all of Hungary Eszakmagyarorszagi Vegyimuvek, Sajobabony, Hungary 22 Filed: May 7, 1973 21 Appl. No.: 357,721

[73] Assignee:

OTHER PUBLICATIONS Smolin et al., STriazines and Derivatives, pp. 292 to 305, Interscience Publishers Inc., N.Y., (1959). Chemical Abstracts Fifth Decennial Index, Subjects Cy-Ey, p. 4078 5, (covering Vols. 41-50 of 19474956 period), (1960).

Primary Examiner-John D. Randolph Attorney, Agent, or FirmYoung & Thompson [57] ABSTRACT 2-Substituted-4-alkylamino-6-(a,a-dimethyl-B- acetyl-ethylamino-l,3,5triazines of the general formula (1) wherein X represents chlorine or a methylthio group, R represents hydrogen or a C alkyl group, and R stands for a C alkyl or alkenyl group, of excellent herbicidal activities are prepared as follows: cyanurchloride is reacted with diacetonamine in a molar ratio of 1:1 in an aqueous or organic solvent medium in the presence of an acid binding agent, the thus-obtained 2,4-dichloro-6-(a,a-dimethyl-B-acetylethylamin0)-1,3,5-triazine is reacted with an amine of the general formula NI-IRR in the presence of an acid binding agent, and if a 2-methylthio compound is, to be prepared, the thus-obtained 2-chloro-4-alkylamino-6-(a,a-dimethyl-B-acetylethylamino)-1,3,5-triazine is reacted with thiourea and the obtained product is methylated, or the Z-chloro compound is reacted with methylthiol.

1 Claim, No Drawings NEW TRIAZINE COMPOUNDS AND HERBICIDES CONTAINING THE SAME, AND A PROCESS FOR THE PREPARATION THEREOF This invention relates to new triazine compounds and to herbicides containing the same, as well as to a process for the preparation of said new compounds and herbicides.

The new 2-substituted-4-alkylamino-6-( agadimethyl-B-acetyl-ethylamino)- l ,3,5-triazines according to the invention correspond to the general formula N N R L J l N NH R!'/ N wherein X represents chlorine atom or a methylthio group,

R represents hydrogen or a C alkyl group, and

R stands for a C alkyl or alkenyl group.

The new compounds of the general formula (I), wherein X stands for chlorine and R and R each have the same meanings as defined above can be prepared as follows: cyanurchloride is reacted with an equivalent amount of diacetonamine in the presenceof an acid binding agent in an aqueous or organic solvent medium, and the thus-formed 2,4-dichlor-6 -(bz,adimethyl-B-acetyl-ethylamino)- l ,3,5-triazine is reacted directly, without any isolation step, with a substituted amine of the general formula Nl-IRR in the presence of an acid binding agent.

In the first step of the above synthesis diacetonamine can also be introduced in the form of its acid addition salt, such as in the form of oxalate, in this instance, however, a base, such as sodium hydroxide or sodium hydrocarbonate is also to be added to the reaction mixture in an amount equivalent to the anion of the salt.

Those compounds of the general formula (I), wherein X represents a methylthio group and R and R each have the same meanings as defined above, can be prepared by reacting the corresponding 2-chloro-4- alkylamino-6-(a,a-dimethyl-B-acetyl-ethylamino)- l,3,5-triazine obtained in the above synthesis with thiourea, and contacting the thus-formed 2-thio compound with a methylating agent. The 2-chloro derivatives can also be converted directly into the corresponding 2- methylthio compounds by reacting them with methylthiol.

We have found that the compounds of the general formula (I) possess herbicidal activities, and can be used for combatting or controlling weeds. in the literature there were already described some alkylamino- 1,3,5-triazine derivatives of herbicidal effects, such as the 2-chloro and 2-methylthio-4,6-bis-alkylamino- 1,3,5-triazine compounds, among which those sold under the trade names Atrazine and Symazine are widely used in the agriculture. The compounds of the general formula (I) have, however, several advantages over the known herbicidal agents of related structures. The new compounds according to the invention show CH H CH selective phytotoxic activities, too, they field of activity, however, differs somewhat from that of the known ones. Namely, the new compounds show greater phytotoxic activities against several weeds than the known ones, and by the alternating use of the known and the new herbicidal agents the development of resistant plant varieties can beavoided and a more effective control of weeds can be ensured.

A further advantage of the new compounds is that they effect appears within a shorter period than that of the known herbicidesof related structure. According to our experiments the effectof the new compounds keto group in the side 'chain, which, due to its protonacceptor character, takes place in the formation of hydrogen bonds.

The compounds of the general formula (I) can be converted'to herbicidal preparations. such as sprays, powders, wettable powders, dusts, granules. etc., and

are used by'applying them in conventional ways to soil 4 as well as tothe foliage of weeds. 1 The rate and method of application, as well as the necessary amount of active agent depends on the effect to be attained. lt is I essential that the active agent should be uniformly distributed in the herbicidal preparations. An amount of l to 10 kgi of active agent pro ha. provides generally satisfactory results. The active agents can be applied onto the soil or plants preferably in the form of liquid sprays or powder dusts. The liquid sprays may be prepared directly at the place of application from emulsion concentrates or wettable powders by diluting them with water. The concentration of the active agent may amount to 0.01 to 5 by weight in the final liquid sprays. The emulsion concentrates or wettable powders used for the preparation of liquid sprays contain carriers and dispersing and/or wetting agents besides the active ingredients. Among the carriers usable for the preparation of wettable powders etg. silicic earth, talc, bentonite, chalk powder or chemical fertilizers are to be mentioned. The carriers are used for the preparation of herbicidal compositions in finely V dispersed state.

The invention is elucidated in detail by the aid of the following non-limiting Examples.

perature not exceeding 5C, thereafter 11.5 g. (0.l mol.) of diacetonamine and finally 4 g. (0.1 mol.) of

sodium hydroxide (as a 10 aqueous solution) are 18.4 g. (0.1 mol.) of cyanurchloride are added to 200 added to the mixture. During the addition the mixture ml f Water with stirring and external cooling, at a temis stirred and maintained at a temperature below 5C. p r r n x ing thereafter g- -1- Stirring is continued for additional 0.5 hours, thereafter mol.) of diacetonamine oxalate, and finally 12 g. (0.3 the temperature of the mixture is allowed to raise to f Sodium. hydroxide a 20 aqueous room temperature. The mixture is stirred at room temtlOh) are added to the t ehe eaction'mixture iS perature for additional one hour. thereafter 13.1 ml. left IOWarm tOTOOm temperature, thereafter g- (0.1 mol.) of a 45 aqueous isopropylamine solution of ethylamine an 50 aqueous i n) n and 4 g. (0.1 mol.) of sodium hydroxide (as a g- H1013) i y x e 10% qu us aqueous solution) are added to the stirred mixture. 1f 10 1,3,5'-triaz'ine are obtained; m.p.: 122134C. The

necessary, the mixture is cooled during addition in Product melts at 1320-1 fter recrystallization order to maintain the temperature below 35C. The obrOm kl lil iXture Of methanol and Water. tained mixture is stirred for 3 hours at room tempera- Analy i Calculatedi Found;

ture, the solids are collected by filtration, washed with N. 26.36 C], 12.96

water, and dried. 20.5 g. (72 of snow-white, crystalline 2-chloro-4-isopropylamino-6-(a,a-dimethyl-B- EXAMPLE 3 acety1-ethylamino)-l,3,5-triazine are obtained; m.p.:

105110C. The product melts at 1 12 1 1 3C after recrystallization from isopropanol. Y

Analysis: Calculated: C, 50.5 H, 5.7 N, 24.6 A mixture of 5.7 g. (0.02 mol.) of 2-chloro-4- CI, 12.4 Found: C, 50.2 H, 5.6 N, 24.9 C1, isopropylamino-6-(a,a-dimethyl-B-acetyl-ethylamino)- l2.04 1,3,5-triazine (prepared as described in Example 1), 40

2-Methylthio-4-isopropy1amino-6-(a,0z-dimethyl-B- acety1-ethylamino)- l ,3 ,5-triazine Similarly can be prepared the following compounds ml. of methanol and 3.1 g. (0.004 mol.) of thiourea is starting from cyanurchloride and the appropriate refluxed for 3. hours. The obtained apolar solution is amine of the general formula NHRR'. left to cool, a solution of 1.6 g. (0.04 mol.) of sodium hydroxide in 3 ml. of water is .added, andthe mixture is refluxed again for 1 hour. Thereafter themixture is Analysis cooled. to 50C, and 2.8g. (0.022.mo1.) of dimethylsul- R r d '1 d. M. Y x R E s fi 12 fat; aatlield inflsmalclktl ortlons at a teimperzlijture of 1 to. g en ea 1 ion 18 Comp ete, t ereact on H f 105-107 67 mixture is refluxed for 1.5 hours, thereafter it is cooled.

C1. 13.7 13.7 (cyclo hexane The solvent is decanted, and the resinous res due 15 Cl y v Cl: 124-126 70 washed with water and dried in air. 3.2 (5 2 of 2- (cyclog r hexane) 'methylth1o-4-isopropylammo-6-(mmdimethyl-B- C 107 iq i 52 35 acet l-eth lamino)-1,3,5-tr iazine are obtained.

3 y Ch 'f 77 Analysisz Calculated: .5, 11.83 c1, 0 %1 Found: s,

EXAMPLE 2 I What'we claim isi 2-Chloro-4-ethylamino-6-(a,a-dimethyl-B-acetyle- 4O 1. A 2-sl.ibstituted-4-alkylamino-6 a ,d-dimethylQB- thy1amino)-1,3,5 triazine acetylethy1arnino)-1,3,5-triazine of the formula solution) are added to the stirred mixture. The mixture wherein is stirred for additional 3 hours. thereafter the sepa- X represents chlorine or a rnethylthio group, rated solids are collected by filtration, washed with wa- R represents hydrogen or a C 2, alkyl group, and ter, and dried. 8.9 g. 66 of snow-white 2-ch1oro-4- 55 R stands for a C, alkyl or alkenyl group. ethy1amino-6-(a,a-dimethyl-B-acetyl-ethylamino)- f g a s j 

1. A 2-SUBSTITUTED-4-ALKYLAMINO-6-(A,A-DIMETHYL-B-ACETYLETHYLAMINO)-1,3,5 -TRIAZINE OF THE FORMULA 